Colour photographic images produced from indazolone colour couplers



United States Patent COLOUR PHOTOGRAPHI'C IMAGES PRODUCED FROM INDAZOLQN E COLOUR COUPLERS John Mathers Woolley, Blackley, England, assignor to Imperial Chemical Industries Limited, a corporation of Great Britain No Drawing. Application March 16, 1953 Serial No. 342,747

Claims priority, application Great Britain March 21, 1952 16 Claims. (Cl. 9655) ,C CO I NH Ne or a tautomeric form thereof, wherein Z represents the non-metallic atoms required to complete an isocyclic, heterocyclic or polycyclic nucleus. The colour image obtained in this way is formed by the coupling of the. oxidation product of the developer on the 2 position of the indazolone ring, that is to say on the N-atom which is in the ortho-position to the carbonyl group. a

We have now found that if instead of the above class of compounds there are used as colour couplers certain 2- substituted indazolones which have not hitherto been known for use as colour couplers, a completely different process of colour coupling occurs.

According to our invention we provide a process for the production of colour photographic images which comprises developing an exposed gelatino-silver halide emulsion layer with a'prirnary aromatic amino developing agent in. the presence of a colour coupler of the formula:

wherein Z represents the atoms required to complete an isocyclic, heterocyclic or polycyclic nucleus and Y represents a substituent from the group consisting of COR, COOR, SO R, CONHR, CONRR', CSNHR, --C(R)=NH, --C(NHR)=NH, -C(NRR)=NH, wherein R and R each represent a hydrocarbon or substituted hydrocarbon radical or a heterocyclic radical.

The colour coupler used in the process of our invention may .be used in the developing solution or it may be included in a light-sensitive layer or in a non-light-sensirive layer adjacent to a sensitive layer or separated therefrom by a water-permeable colloid layer.

' It is a preferred feature of our invention to include the colour couplers in one or more light-sensitive gelatinosilver halide emulsion layers which form part of a multilayer film or paper of the kind used for colour photography. For this purpose it is preferred to use colour couplers which contain a substituent rendering them fast 5, to diffusion, for example an alkyl chain of at least 5 carbon atoms and, if desired, a solubilising group.

The colour couplers used in the process of our invention may be made by the general processes known for use in the synthesis of substituted indazolones or by treating the appropriate indazolone by processes known for replacing a hydrogen atom attached to a nitrogen atom by the radicals indicated by Y in the above formula. The parent indazolone which may be substituted in the benzene nucleus, for example by alkyl, alkyloxy, aryloxy, nitro, halogeno, amino, or acylamino, may for example be made by causing a molecule of water to split off from the appropriate o-hydrazino-benzoic acid, for example by heating the latter in dilute hydrochloric acid, and the hydrogen atom attached to nitrogen in the 2-position can then be substituted.

For example when Y is --COR, COOR, SO R,

CONHR, CONRR' or CSNHR in the above for mula the colour couplers may be made by treating the appropriate indazolone in boiling toluene with the appropriate acid chloride, chloroformic ester, sulphonyl chloride, isocyanate, di-N-substituted carbamyl chloride or isothiocyanate respectively.

The colour couplers used in the process of our invention have advantages over the known indazolone colour couplers which contain no substituent in the 2-position in that they are more resistant to oxidising agents and they do not give yellow oxidation products in the bleaching bath used for removal of silver.

Specific examples of suitable colour couplers are 2- carbethoxy-indazolone, Z-phenylcarbamyl-indazolone, 2- naphthylcarbamyl-indazolone, Z-phenylthiocarbamyl-indazolone, Z-stearoyl-indazolone, 2-(p-toluene-sulphonyl)- indazolone and Z-phenylethyl carbamyl-indazolone. Other specific compounds are mentioned in the examples below.

The aromatic amino compounds which may be used as developing agents in the present invention include the mono-, diand tri-amino-aryl compounds. Among the mono-amino developing agents may be mentioned aminophenols and amino-cresols and their halogen derivatives and amino-naphthols. I

The developing agents preferably used and giving the best results in connection with the present invention are the aromatic orthoand para-diamines such as paraphenylene diamine and its substitution products.

The colour coupling which occurs in the process of our invention when an exposed gelatino-silver halide emulsion is treated with a primary aromatic amino developing agent in the presence of an indazolone substituted in the 2-position, proceeds by a surprising and wholly unexpected reaction in which the indazolone ring is split and an azo dyestufr' is formed in which the residue of the oxidation product of the developing agent is attached to the nitrogen atom which previously formed the l-nitrogen atom of the indazolone ring. For example when 2phenylcarbamyl-indazolone is used as the colour coupler and p-diethylaminoaniline is used as developing agent a dyestuff is formed which is believed to have the following formula:

Itwill be noted that the substituent on the nitrogen atom in Z-position of the indazolone ring is vno'tsp'lit off during colour development.

u: According to a further feature of our invention therefore we provide a colour photographic element which contains in at least one emulsion layer a colour image comprising a dyestufr of the formula:

C O-NH-Y N=NX and it will also be apparent that by suitably after-treating the residual colour coupler, left after colour development, a colour correcting masking image can be formed, or by selecting colour couplers which are themselves coloured, the residual colour coupler left after colour development can itself be utilised as a colour correcting masking image.

The dyestuff images formed by the process of our invention are superior to the known azamethine images in their chemical stability and their fastness to light and the process of our invention provides a simple method of obtaining colour photographic images of good fastness properties by direct development of an exposed gelatinosilver halide emulsion with aromatic amine colour developers.

The invention is illustrated but not limited by the following examples in which the parts are by weight:

Example 1 Two solutions are prepared with the following compositions.

1 part of 2-carbethoxy-indazolone is dissolved in 500 parts of Solution B. 500 parts of Solution A are added and the solutions are well mixed to form Solution C. A light-sensitive gelatino-silver halide emulsion layer on a support is exposed to light and then developed in Solution C. The developed silver and residual silver halide are removed by bleaching and fixing when an orange image having an absorption maximum at 480 m is obtained.

When the p-diethylaminoaniline sulphate used in the above example is replaced by an equal weight of 2-methyl- 4-diethylaminoaniline, an orange-red image is obtained having an absorption maximum at 500 mu.

Under similar conditions the parent indazolone gives a bluish magenta dyestuff with an absorption maximum at 542 me, when p-diethylaminoaniline is used as developer.

The Z-carbethoxy-indazolone used in the above example is prepared as follows:

6.8 parts of indazolone are added to 160 parts of toluene. The mixture is stirred and 6 parts of ethyl chloroformate are added. The mixture is stirred and boiled under a reflux condenser for 1 hour. The hot mixture is allowed to settle, and the supernatant liquid is decanted from the syrupy oil and allowed to cool. The 2-carbethoxy-indazolone which crystallises out is filtered olfand dried. Theproduct melts at 140 C.

Example 2 1 part of 2-phenylcarbamyl-indazolone is dissolved in 160 parts of methanol. parts of Solution B described in Example 1, 20 parts of sodium acetate and 100 parts of Solution A described in Example 1 are added. The mixture is stirred until complete solution is obtained. A light sensitive gelatino-silver halide emulsion layer mounted on a support is exposed to light and developed in the above solution. The film is bleached and fixed when an orange image having an absorption maximum at 484 m is obtained.

Instead of the 2-phenylcarbamyl-indazolone used 1n the above example, Z-u-naphthyIcarbamyl-indazolone can be used when an orange image is formed. When this Z-tx-naphthyl compound is used the sodium acetate can be omitted from the developing solution.

The Z-phenylcarbamyl-indazolone used in the above example can be prepared as follows:

1 part of indazolone and 1 part of phenyl isocyanate are mixed together and 60 parts of butanol are added. The mixture is boiled gently under a reflux condensen until a clear solution is obtained. The solution is then allowed to cool and the 2-phenylcarbamyl-indazolone which crystallises out is filtered off, washed with ether and dried. The product forms colourless needles melting at 218 C.

The corresponding 2-a-naphthyl compound can be similarly prepared from a-naphthylisocyanate.

Example 3 In place of the 1 part of Z-phenylcarbamyl-indazolone used in Example 2, there may be used 1 part of 2-phenylthiocarbamyl-indazolone when an orange image is obtained. 2-phenylthiocarbamyl-indazolone may be prepared as follows:

1 part of indazolone and 1 part of phenyl isothioisocyanate are added to 20 parts of toluene. The mixture is boiled under a reflux condenser for 30 minutes. The hot mixture is filtered and the filtrate is cooled when the product separates in the form of yellow crystals melting at 228 C. i

Example 4 In place of the 1 part of 2-phenylcarbamyl-indazolone used in Example 2 there may be used 1 part of 2-stearoylindazolone when an orange image is obtained. Z-stearoylindazolone may be prepared as follows:

A mixture of 850 parts of stearic acid, 400 parts of indazolone, 137 parts of phosphorus trichloride and 10,000 parts of toluene is boiled under a reflux condenser for 1 hour. The reaction mixture is allowed to settle and the hot supernatant liquid is decanted from the tar and allowed to cool. The 2-stearoyl-indazolone which crystallises out is filtered 0E. The product is recrystallised from ethyl acetate when it melts at 122 C.

Example 5 Example 6 In place of the 1 part of Z-carbethoxy-indazolone used in Example 1, 1 part of 2-(3-sulphobenzoyl)-5-chloroindazolone may be used. This colour former may be obtained by reacting 3-chlorosulphonyl-benzoic acid with chloroindazolone in boiling toluene.

Example 7 6.7 parts of indazolone are dissolved in 100 parts of dioxane and a solution of 18.5 parts of octadecyl chloroformate in 42 parts of chlorobenzene is added. The suspension so obtained is boiled under a reflux condenser until a clear solution is obtained and no further evolution of hydrogen chloride occurs. The mixture is cooled and the white solid in suspension is-filtered off and washed firstly with cold methanol and then with ether and finally dried. The 2-carboctadecoxy indazolone so obtained is incorporated into a lightsensitive gelatino-silver halide emulsion and the emulsion is coated on a film base and dried; The light-sensitive film so obtained is exposed to light and developed with 2-methyl-4-diethylamino-aniline. The film is then bleached and fixed and an orange dyestufi image of maximum absorption 500 m is obtained.

,In place of the colour former used in the above example, 2-carboctadecoxy-5:7-dibromo-indazolone may be used when a redder dyestufi image with maximum absorption at 520 m, is obtained.

Alternatively, in place of the colour'former used in the above example there may be used 2-carboctadecoxy-4- chloro-, 5-chloro-, 6-chloro-, 5-bromo-, 5:7-dichloro-, 5- nitro-, 6-nitro-, 5-methoxy-, 6-methoxyor S-phenoxy-indazolones (which like the 5:7-dibromo compound mentioned above may be made by the action of octadecyl chloroformate on the parent indazolones carrying appropriate substituents in the benzene ring, which themselves may be made by the action of a dehydrating acid on the appropriate o-hydrazino-benzoic acids), 2-carboctadecoxy- 5acetylamino-, or 6-acetylaminoindazolones (which may be made in a similar manner from the acetylaminoindazolones which themselves may be made by acetylating the aminoindazolones), 2-(4'-dodecylphenyl)carbamyl-indazolone and the corresponding S-bromo compound which may be made by the action of p-dodec'ylphenylisocyanate on indazolone and S-bromo-indazolone respectively, 2-(4-dodecylphenyl)-carbamyl-5-(4'-dodecylphenylureido)indazolone which may be made by the reaction of S-aminoindazolone with two molecular proportions of p-dodecylphenylisocyanate, or the alkali soluble compounds Z-octadecenyl-succinyl-indazolone (which may be made by the action of octadecenylsuccinic anhydride on indazolone) or 2-carbethoxy-5octadecenylsuccinyl-amino-in'dazolone which may be made by the action of ethyl chloroformate on 5-octadecenylsuccinyl-aminoindazolone.

What I claim is:

1. Process for the production of colour photographic images which comprises developing an exposed gelatinosilver halide emulsion layer with a primary aromatic amino developing agent in the presence of a colour coupler of the formula:

' layer.

4. A light sensitive gelatino silver halide emulsion layer containing a colour coupler of the formula:

- R and R each represent a member of the group consisting of hydrocarbon, a sulfo-substituted hydrocarbon radical and a heterocyclic radical.

5. A light sensitive gelatino silver halide emulsion layer according to claim 4 which contains a substituent rendering the colour coupler fast to difiusion and a solubilising group.

6. Process for the production of colour photographic images which comprises developing with a colour forming developer an exposed gelatino silver halide emulsion .layer containing a colour coupler of the formula:

wherein Z represents the non-metallic atoms required for completing an aromatic nucleus, and Y represents a substituent from the group consisting of --COR, COOR, -SO R, CONHR, CONRR and CSNHR wherein R and R each represent a member of the group consisting of hydrocarbon, a sulfo-substituted hydrocarbon radical and a heterocyclic radical, said colour coupler containing a substituent rendering the colour coupler fast to diffusion and a solubilizing group.

7. The process of claim 1, wherein the colour coupler is selected from the group consisting of unsubstituted and substituted indazolone compounds, wherein the substituent is designated by the letter R and is selected from the group consisting of a halo group, a hydrocarboxy group, a nitro group, an acylamino group and a hydrocarbonureido group attached to the benzene ring of the indazolone nucleus, said compound having the formula o l R El \NY wherein Y represents a substituent from the groupconsisting of COR, COOR, SO R, -CONHR, --CONRR', CSNHR, wherein R and R each represent a member of the group consisting of a hydrocarbon, a sulfo-substituted hydrocarbon radical and a heterocyclic radical.

8. The process of claim 7, wherein R and R are both hydrocarbon radicals.

9. The process of claim 1, wherein the color coupler is an unsubstituted indazolone compound of the formula wherein Y represents a substituent from the group consisting of COR, COOR, -SO2R, CONHR,.

7 --CONRR', --CSNHR, wherein R and R each represent a member of the group consisting of a hydrocarbon, a sulfo-substituted hydrocarbon radical and a heterocyclic radical.

10. The process of claim 1, wherein the color coupler is Z-carboctadecoxy indazolone.

11. The process of claim 1, wherein the color coupler is Z-carbethoxy indazolone.

12. The process of claim 1, wherein the color coupler is 2-phenylcarbarnyl indazolone.

13. The process of claim 1, wherein the color coupler is Z-phenylthiocarbamyl indazolone.

14. The process of claim 1, wherein the color coupler is Z-stearoyl indazolone.

15. A process for the production of colored photographic images which comprises developing an exposed gelatinosilver halide emulsion layer by means of a primary aromatic amino developing agent in the presence of a color coupler of the formula:

Q and tautomeric forms thereof, wherein Z represents the non-metallic atoms required for completing an aromatic nucleus, and wherein Y represents an acyl group.

16. A light sensitive gelatino-silver halide emulsion layer containing a color coupler of the formula:

/GOO

and tautomeric forms thereof, wherein Z represents the non-metallic atoms required for completing an aromatic nucleus, and wherein Y represents an acyl group.

References Cited in the file of this patent UNITED STATES PATENTS 

1. PROCESS FOR THE PRODUCTION OF COLOUR PHOTOGRAPHIC IMAGES WHICH COMPRISES DEVELOPING AN EXPOSED GELATINOSILVR HALIDED EMULSION LAYER WITH A PRIMARY AROMATIC AMINO DEVELOPING AGENT IN THE PRESSURE OF A COLOUR COUPLER OF THE FORMULA: 